Dyeing of cellulose esters and ethers



Patented Aug. 27, 1935 UNITED STATES DYEING OF CELLULOSE ESTERS AND ETHERS Frankfort-on-the-Main-Hochst, to General Aniline Works, Inc., New York, N. Y.,

Erwin Thoma,

Germany, assignor ware No Drawing.

Serial No. 1932 The present invention relates to the manufacture of dyeings on fibrous materials made of cellulose esters or ethers and to the dyed materials,

.more particularly it relates to a process which comprises applying'to the said fibrous materials 7 a suitable amino compound, free from sulfonic acid'groups, capable of forming a diazo component, diazotizing the amino compound on the fiber and developing (coupling) with a 5-keto-4.5-dihydropyrazole compound of the general formula:

wherein R1 stands for a radical of the benzene series and R2 for COOH, CONHz, CONH-aryl, or for an esterifled carboxylic acid group.

The technical advance attained according to the present invention resides in the fact that the dyeings produced on fibrous materials made of cellulose esters or ethers by means of the above defined group oi 5-keto-4.5-dihydropyrazole compounds possess good fastness properties and can be well discharged, yielding excellent white discharge effects when treated with reduci-ng discharging agents in known manner. Developing components of such propertiesare highly desired in the art of dyeing cellulose esters and ethers by means of the class of the so-called developing dyes.

Thedyeings obtainable, for instance, by coupling on the fiber a diazotized' amino compound with 1-phenyl-3-methyl-S-pyrazolone cannot be discharged or can only insufliciently be discharged a corporation of Dela- Apnlication November 29, 1933, 700,367. In Germany December 3,

6 Claims. (Cl. 85)

dyeings obtainable from l-nitroaryl-3-methyl-5- pyrazolones, for instance, from l-metaor 1- para nitrophenyl 3 methyl 5-pyrazolone, according to German Patent No. 284,695, also cannot be sufiiciently discharged.

The production of the dyeings may be carried out in the usual manner. For instance, a dye-bath is prepared by dissolving about 1% of the amino compound, calculated onthe weight of the goods,

in water while adding a suficient quantity of hydrochloric acid or formic acid to obtain a solution. In this solution acetate silk or other textile material made of cellulose esters or ethers are handled while slowly raising the temperature and heating for about /2 to 1 hour at about 50 C. to about 75 C. To the dye-bath about 5% to 10% of sodium acetate, calculated upon the weight of the goods, are advantageously added during the dyeing operation. Thereupon, the material is diazotized on the fiber in the 'usual manner in a freshly prepared bath, and the dyeing is then developed for about A at about 50 C. to about 75 C. in anothertbath having a neutral or weak acetic acid reaction and containing the necessary quantity, say 3 per cent, of the 5-keto-4.5-dihydropyrazole compound, calculated upon the weight of the goods.

The amino compound may alternatively be used in the form of a suspension or emulsion in a soap bath or in the presence of any other dispersing medium. The amino compound may then be diazotized and the dyeing be developed as above described.

In the following table a number of dyeings, obtainable according to the present invention, is disclosed. It is, however, understood that the invention is not restricted to the particular comby means of reducing discharging agents. The binations shown:

Diazo component Coupling component Tint l-phenyl-5-keto-4.5-dih dro yrazole-a-carboxylic acid Orange-yellow. 1 O O methyl ester. y p 2 D l-pheiiliiyl-5-keto-4.5-dihydropyrazole-3-carboxylic acid Orangared;

- am e. 3 D 3-methyl-5-keto-4.5-dihydropymzole Gold-yellow.- 4 D 5-keto-4.5-dihydropyrazole-3-earboxylloacid Orange. 15 D 5-keto-4.5-dlhydropyrazole-3-carb0xyllcacldethyl ester. 7 Do. a o l.3-dlmethyl-5keto-4.s-dlhydropyrazole Gold-yellow. D 3-pl enyl-5-keto 4.s-dihydropyrazole...'... Orange. s pn 5-keto-4.5-dihydropyrazole Yellow. 9 Dn li-keto4.5-dihydropyrazole-3Pcarboxylicacid amide Orange-red. 10 D zfiplienyl-5-keto-4.5-dil1ydropyram1e-1- nrboxylic acid Gold-yellow.

ethyl ester. Q 3-methyl-5-keto-4.5-dlh dro yrawle-l-earboxylic acid Do. u O O unmet. H D 1-methy1-3-phenyl-5-keto-4.154llhydropyrazillen... Orange-yellow.

to about 1 hour' Diazo component Coupling component Tint 13 O I 1-methyi-5-keto-4.5-dihydropyrezole.-, Gold-yellow. 14 Do 1-znethyl-5-keto-4.5-d1hydropyruole-3-carboxylic acid Orange.

, ethyl ester. 15 Do l-met layl-ii-keto-4.5-dihydmpymzole-3mrboxylle acid Do.

am e. 16 D l-ortho-nitm henyl-5-keto-L5-dlh dro yrazole-carbox- Gold-orange;

/ acid 6813'] ester. y p I 17 EN 9 3-methyl-5-ket0-4.5-dlhydropymzole Gold-yellow.

Ha H: OCH: 000K. l-phenyl-iS-keto-Lii-dihydropyrazole-li-eerboxylic acid Reddlsh-omnle. methylesiet. 18 EN N=N 19 Do l-phenyl-IS-keto-iJ-dihydropyrezoleh-eurboxylic ecid Orange-red.

, ethyl ester. 20 Dn lgl ig rayH-kemfidihydmpyrazole-euboxylic ecid Do.

0. I 21 Do l-gfiflngM-keMzB-dihydropymzole-(i-carboxylic acid Scarlet.

e. 22 on 5-keto-4.5-dlhydropyruole-3-carboxylic acid -Q Red-orange 23 D 7 5-keto-4.5 iihydmpymole-3-cerboxylic acid ethyl ester" Do. 24 D 3-methyl-5-keto-4.5-dihydropyrazole-l-earboxylic acid Gold-orange.

ethyl ester. 25 D 3-nnmfgl-5-keto-L5-dihydmpyrmle-1-cerboxylio ldd Onnge. as D a ghltlniila'i-kemfi-dihydropymole-l-mrboxylio mid D0. 27 D l-phenyl-fi-keto-ifi-dlhydropyrolole-euboxyuo odd.-. Beddish-otma. 28 Pere-nitrmnilin l-plti ilan y l liu-hreto-Lii-dihydropymo' le-z-earboxylic ecid Greenish-yellow.

- CH; 3-methyl+keto-L6-dihydropymole-i-cuboxylie acid Ballet-red. a m O aniiide.

Q 01 CH: ao' D l-myl-a-nms-dmydmmole-a-mbox ue eeid Bed-brown.

. e. 31 D l-phenyl-li-keto'iMlhydropyruomboxylic acid Currant.

methyl ester. 32 D IJ-dImethyIWMB-dihydmpymmlo Bed. 83 D a-phcnyl-ii-kemb-dihydropyruolenn' Violet-brown. 34 D ii-keto-Lfi-dihydropyrmlo-B-mrboxyllcedd Violet. 35 D Y l-methyl-a-phenyl-o-keto-u-dlhydxopyruolefle. Bluilh-led. 36 1- hen l-li-heto-M-dih dro ynzolo-a-eubo lic Current.

O gthyfemr. y p

87 D I B-methylMiB-dihydmpynzole Brown-red. t8 1-methyl-5-keto-4.5-dihydm ynzoio-a-cerboxylio acid Gold-yellow. O 'O methyl m. p no i-mun l-smsdm dmpmmlmmue add"- Oren.

, N-N NN 40 n Hood-5 co 0c 5-0001! 0mm O C OOH: 000E -.--.do D0. b d

I .....do 3m By replacing in the above defined combinations the amino-azc-compounds, used 'as diazo compo-. nents, by other amino-azo-compounds, tor instance tho'se which contain alkyb, halogem,

nitroand dialkyl-amino groups, or by diaminoazo-aryl compounds, or by diamino-aryl compounds, such as dianisidine, tolidine, etc mono-amines, such as naphthylor by amine, para .Iclaim:

nitraniline or others, there are obtained dyeings which, in contradistinction to those which are obtainable by means or the same bases and with 70 1-pheny1-3-methyl-5-pyrazolonea can well be dilcharged, yielding white discharge eflecte.

1. A process of producing dyeinsl onn'broue materials or the group eoneieting of cellulose l wherein R1 stands for a radical of the benzene series and R2 for a substituent selected from the group consisting of COOH, CONHz, CONH-a'ryl and an esterified carbdxylic acid group.

2. A process of producing dyeings on fibrous materials of the group consisting of cellulose esters and ethers, which dyeings can be well 'discharged, which comprises applying to the material an amino-monoazo dyestufi' of the benzene series, free from sulfonic acid groups, diazotizing the amino compound on the fiber and developing with a coupling component of the general formula:

wherein R1 stands for a radical of the benzene series and R2 for a substituent selected from'the group consisting of COOH, CONI-Iz, CONH-aryl and an esterified carboxylic acid group.

3. A process of producing dyeings on acetate silk, which dyeings can be well discharged, which comprises treating acetate silk in a bath containing 4-amino-3-methoxybenzene-azo-3'-carboxybenzene, diazotizing on the fiber and coupling with 1-phenyl-5-keto-4,5-dihydropyrazole-3-carboxylic acid ethyl ester.

4. Fibrous materials of the group consisting of cellulose esters and ethers, dyed with dyestuffs according to claim 1.

5. Fibrous materials of the group consisting of cellulose esters and ethers, dyed with dyestuffs according to claim 2.

6. Acetate silk dyed with dyestuffs according to claim 3.

ERWIN THOMA. 

